Electric current rectifier



Jan. 31, 1933. s. RUBEN ELECTRIC CURRENT REGTIFIER Filed Dec. l, 1928 Cu. CuzO uS Patented Jan. 3.1, 1933 UNITED STATESA PATENT vola-Ica SAMUEL RUBEN, OF NEW YORK, N. Y., ASSIGlNOB. TO RUBEN RECTIEIER CORPORATION,

I OF ENGLEWOOD, NEW JERSEY, .A CORPORATION OF DELAWARE ELECTRIC CURRENT RECTIFIER #Application Bled December 1, 1928. Serial No. 323,084. i

This invention relates to electric -current `rectiiers and the like, which employ electrode elements of the dry type, and more particularly to rectiiers of this character which employ electrode elements so formed that each constitutes a unitary rectifying cell. y

Rectifiers of this type are known in which the electrode elements are a composite body of a metal coated intimately with an oxidel compound thereof, in a4 manner which develops a. rectifying junction at the surface which is overlaid by the compound. Such rectifiers depend for their operation upon the asymmetric resistance characteristics which obtain at this junction.

The .present invention has for its object generally the provision of an improved device of he character described, which is eflicient, economical and readily manufactured.

More specifically, it is an object to provide a rectifying electrode element which is more suitable than the prior art devices, for example, one which is capable of withstanding higher operating voltages and temperatures and at the same time has a more uniform distribution of resistance at the rectifying junction.

It is also an object to provide a rectifying element which is adapted for operating under a .greater range of differences of impressed potential than is applicable to elements of copper which have a coating of cuprous oxide. It is still a further object -to provide a lunitary electrode element which has additively the asymmetric conductivity of a plurality of junctions, for example, the asymmetric conductivities of both"copper oxide andcopper sulphide junctions with metals? Other objects of the invention will in`part be obvious and will in part appear hereinafter.

This case is a continuation, in part, of my co-pending application Serial No. 283,217, filed December. V6, 1927.

features of construction, combinations o'f elements, and arrangement of parts, which willA be exemplified in the 4constructions hereinafter set forth and the sc ope of the applilarged to show schematically the component The invention'accordingly comprises thecation of which will be indicated in the claims.

For afuller understanding of the nature and objects of the invention reference should be had to the following detailed description taken in connection with the accompanying drawing, in which:

Fig. 1 showsdiagrammatically a rectifying device-employing electrode elements constructed in accordance with the present i11- vention connected in a bridge circuit for rectifying alternating current;

Fig. 2 represents a cross Section of an electrode element of the present invention en parts thereof;

Fig. 3 1s a crossA section ofan electrode element of the present invention atan intermediate stage in the process of its manufacture; l

Fig. 4 shows a modied form of electrode l element constructed in accordance with the invention and Figs. 5 and 6 show schematically the manner in which electrode elements of the character shown in Fig.- 4, may be connected in a circuit for effecting half-wave rectification of an alternating current.

Referring now to the drawing, and particularly to Fig. 1, 10 and 10 denote respectively electrode elements constructed as hereinafter described, which are adjacently disposed for series operationl and'comprise an arm of a bridge-connected rectifying unit that receives Aalternating current from av 85 source of supply here denoted conventionally at 11. Such source has a greater difference' of potential than it is desired directly to impress across the arms of the bridge-rectifying circuit. A step-downA transformer 12 is accordingly interposed between the source 11 and the input terminals 13 and 14 ofthe rectifying unit, these terminals being connected across the low-tension side of the transformer 12. The other-arms of the bridge' circuit are similarly constructed of series-connected rectifying elements of the character shownY at 10 and 10', the four arms being arranged in pairs to comprise\two groups of elements which have the input electrpdes 13 and 14 dis- 100 posed therein at intermediate points, the of a non-oxidizing nature and maybe, for groups being connected in inverted relation example, a mineral oil or hydrochloric acid. with respect to each other between conduct- The' copper plate thus treated has formed ing standards 15 and 15', which also serve a's thereona dense homogeneous crystalline layan output terminal and are connected toer of cuprous oxide intimately and uniformgether by means of the conducting rod 16 ly attached over the surfaceof the copper sheathed in an insulating tube 17 so as not base. to short-circuit the electrode elements. The In order that the electrode element shall end of this rod, indicated at 18, serves as have superposed layers of two different comthe connecting means for one direct-current pounds 'of the Sixth Periodic' group, 1t 1s 75 output terminal, whereas the other terminal thereafter subjected to a treatment by'which of the output circuit is shown at 19, which is a second layer is superposed upon the lirst. here formed as an extension of the eonduct- This 1s conveniently accomplished by' taking ing plate 19', interposed between the inverted the plates whi h have been oxidized and exgroups of the electrode elements.` posing them, in a closed reaction chamber, to 90 Fig. 2 illustrates an enlarged cross section the vapors of another compound of the Sixth of the electrode element shown at 10. These Periodic group, for example, the vapors of' electrode elements comprise a metallic backsulphur heated to -a temperaturev of about ing 20, which is of highly conducting metal 425 C., the pressures of the vapors in this 20 and is adapted to form compounds with the reaction chamber being preferably material- 85 chemical elements of the o gen family in 1y about atmospheric, Snell treatment iS the Sixth Periodic group. Elch metal may preferably continued for a period of substanbe, for example, tantalum silver or copper; tially five minutes, when a portion of the copper, however, is preferred. On theback-v oxide coating at the surface of the copper ing 20 there is formed an intimate crystalbase is converted into a sulphide by the 90 line layer of an oxide of the metal. This process of substitution, cupric sulphide belayer is indicated at 21. In intimate contact ing the compound formed at the temperature with the layer 21, there is superposed a second indicated. At the completion of the reaction layer 22, which is a substitution compound period, the electrode element is withdrawn formed with another element of the oxygen from the reaction chamber and allowed to 95 family in the Sixth Periodic group. cool relatively slowly. Examination shows A coated metallic body of this character v that as a result of this latter treatment, there constitutes a composite rectifying element iS SllpelpOS'ed llpOn tile OXide. lil-yer a relativehavingconjointly the advantages of a pluly dense homogeneous layer of blue cupric rality of compounds of the chemical elements sulphide.

of the Sixth Periodic' group. Such a rectify- A Copper body formed for service an ing element may be assembled in the rectifyelectrode element in this manner is,of course, ing unit'shown in Fig. 1 between two e011- uniformly coated on all sides with layers of ducting plates such 'as shown at, 23 and 23', the character indicated, a cross section of an 40 which effect electrical contact with the receleCiIOde element at this Stage being iilllS- '105 tifying element. It 'is found in practice, trated in Fig. 3, where 30 denotes a core comhowever, that it is preferable to interpose prisng a plate of substantiallypure copper; between the coated side of the electrode ele- 3l denOteS a Crystalline layer` 0I' envelope 0f ment and the terminal plate 23, a buii'er- Cuprous Oxide, and 32 an outer layer or encontacting element such as shown at 24 in velope of cu'prlc sulphide. 110

Fig Q A\ Such buifelncontacting element, is l III Order t0 OI'III this Coated lIltO all made of a, relatively soft mei-,a1 which is Subelectrode element comprising a .copper plate stantially inert as a rectifying element and coated only on one side with oxide and sulis without polarizing efeet, Lead has been phide layers, it ispreferably machined to reascertained to be a suitable material for the IIIOVe the Coatings from 011e Side and eXPOSe 115 butler-contacting plate 24. the free surface of the copper. Any suitable Where copper is employed as the metallic modeof machining may be accomplished, for base to be coated in order` to provide a recexample, grmding.

tifying element as shown. 1n Fig. 2, a clean Where a single element is to be employed copper plate is first preferably oxidized by to accomplish the rectifying effect, and it is 129 heating in an oxidizing atmosphere substannot desired to assemblein Operative relation tially to 1,0000 C. This oxidizing atmosa plurality of rectifying elements in order phere, when at a pressure of substantially one to form a rectifyng unit, it is not necessary atmosphere, will produce a layer of cuprous that the coatings be removed from one side ao oxide of a desired thickness if the reaction of the coated plate as above described, since period be maintained for substantially five the'element may be formed with a projecting minutes. When thus treated, the electrode Conducting prong, asY indicated at 33 in Fig. i element is quickly withdrawn from the reae. 4, through which conducting relations may tion chamber and plunged into a quenching be eiected-with the copper plate. The other e5 bath of cooling fluid. Such a bath should be terminal of the rectifying circuit is, of course, 130

made by direct contact with the surface of the outermost;y coating 32. The manner inl which this is accomplished is shown in Fig. 5, where the tab or prong 33 is connected to a conductor 35, and a conductor 34 is se-v cured in direct conducting relation with one side of the coating 32. A rectifying circuit connected in this manner, is shown in full in Fig. 6, the rectifying element in side elevation. Here 41 represents an A. C. supply, 42 a step-down transformer, 33 and 34 the terminals of the rectifying element, a loa-d which is supplied with rectified current beinv indicated at 38, Y

In operation, when the input terminal 13,

l is supplied with alternating current of positive polarity, current passes from this terminal through the rectifying elements 10 and 10 on the left to the conducting standard 15 which connects through conducting bolt 16, with the terminal 18 to supply direct current to the positive terminal of the load. From the negative terminal of the load, current continues its passage through the terminal 19 of the rectifying unt and thence through the pair of electrode elements which comprise the arm shown o n the right of the plate 19 to the alternating current input terminal 14 and thence to the source of sup ply. The passage of the positive component of the current is thus seen to traverse successively the cupric sulphide layer, the cuprous oxide layer and the copper.. One rectifying junction obtains between the layers of cupric sulphide and cuprous oxide and a second junction between the layer of cuprous oxide and the copper backing. The passage of current is accompanied by a drop of potential at both of these junctions, which is evidenced by the fact that there is a greater drop where this composite electrode element is used than would occur at a single junction of either variety. It is thus permissible to impress greater differences of potential across electrode elements of this character than across ysingle rectifying junctions. It is also found by this arrangement that increased stability in the rectifying output is achieved.

While the passage of current has been traced for the circuit shown in Fig. 1, it is obvious that a similar passage takes place for the circuit shown in Fig. 6, where, if the lower terminal of the alterna-ting current source has positive polarity, a direct current will pass through the load at 38 and thenceJ through the conductor 34 through the coatings on the rectifying element to the copper backing 30, and thence by way of prong 33 and Conductor 35 to the source of supply.

' The step of quenching as herein practiced,

provides an electrode element having s uperior characteristics to ordinary electrode elements of copper coated with cuprous oxide, since vthe electrode elements thus quenched have a relatively clean surface of'cuprous oxide and the crystalswhich compose the cuprous oxide layer also adhere very intimately with the metallic backing or so-called mother metal. In this manner the resistance of the electrode element is reduced, particularly the conta/ct resistance.

Cuprous oxide, it has been ascertained, is one ofthe crystalline conductors that has a relativelywide variation of contact resistance with pressure. If, characteristic curves be.

ydrawn showing the correlation betweenreresistance with pressure in ycuprous oxide coated electrode elements is substantially compensated for by providing an intimately joined layer of cuprous sulphide, as herein provided. The use of the lead contact washers also appears to assist in nullifying any variation of resistance with pressure.

By the present invention it is thus seen that rectifying elements are provided which are relatively constant in their operating characteristics; agingl also may be substantially dispensed with in order to reach stable operating conditions; and the losses incident to linternal resistance are very materially reduced. A

Since certain changes may be made in the Y above construction and different embodiments of the invention could be made withouty departing from the scope thereof, it is intended that all matter contained in the above description or shown in the accompanying drawing shall be interpreted as illustrative and not in a limiting sense.

Having described my invention, what I claim as new and desire to secure by Letters Patent, is:

1. In dry rectifying devices and the like, an electrode element therefor comprising a lmetallic base, an intimately joined oxide thereof intimately joined with said metallic lbase and. adapted to provide a iectifying junction at the contacting surface with said v metallic base, and a sulphur compoundof rectifying junction.

4f.V In dry rectifyingdevices and the like,

an electrode element therefor comprising a yIsis backing of metallic copper, an intimately joined layer of cuprous oxide overlying a surface of said copper backing and providing a rectifying junction at said surface, and a layer of a sulphur compound of copper overlying said cuprous oxide layer and forming a second rectifying junction at the contacting surfaces of said compounds.

5. In dry rectifying devices and the like, an electrode element therefor comprising a backing of metallic copper, a laye'r of crys-I talline cuprous oxide intimately joined to said copper backing` and proyiding a rectifying junction at the surface where joined, and a layer of cupric sulphide overlying said oxide layer and intimately joined thereto and adapted to provide a second rectifying junction at the juncture of said compounds.

6. In dry reetifying devices and the like,

an electrode element therefor comprising abacking of metallic copper, and a layer of crystalline cuprous oxide on a surface of said copri-fr backing and intimately joined thereto and formed to provide a rectifying yjunetion; a portionlof the outer surface of said crystalline layer being converted intoa sulphur compoiwd whereby a second rectifying junction is provided in series with the first.

7. In dry rectifying devices l' and the like, an electrode element therefor comprising al metallic backing, and a crystalline layer of an oxygen compound of the metal in said backing intimately joined to a surface of said backing and forming a rectifying junction therewith; a portion of the outer surface of said crystalline layer being converted to a sulphur compound whereby a- 'second rectifyvng junction is provided in series with .the rst. 8. The method of forming electrode elements for dry rectifiers and the like, which comprises heatinga metallic body in an atmosphere containing an element of the oxygen familyin the Sixth Periodic group until a relatively thick compound thereof is formed thereon, quenching said heated element, again'heating said. electrode element vin an atmosphere containing a second chemical elecomprises heating ing said heated body,

ment of the Sigth Periodic group, and thereafter cooling said element.

9. The method of forming electrode eleoxygen compound is formed thereon, quenching said heated element, again heating said electrode element in an atmosphere containing a chemical element of the oxygen family in the Sixth Periodic group other than oxygen, and thereafter cooling said body.

10. The method of forming electrode elements for dry rectifiers and the like, which a metallic body in an oxidizing atmosphere until a relatively thick oxygen compound is formed thereon, quenchthereafter heating said body iii an atmosphere containing a chemical element of the oxygen family in the Sixth Periodic group other than oxygen, and thereafter permitting said lieat-ed body* to cool slowly.

-ments for dry rectifiers and the like, which comprises heating` a copper plate in an oxidizing atmosphere to a temperature of substantially 1000o C. until a relatively thick oxide coating saidv coated electrode element in a non-oxidizing bath, and again heating said coated element in an atmosphere containing sulphur vapor until a relatively thick outer layer of a sulphur compound has been formed, and thereafter permitting said electrode element to cool.

l2. The method of forming'electrode elementsvfor dry rectifiers and tlie like, which comprises heating a plate of copper in an oxidizing atmosphere to a temperature of substantially 1000 C. for a period of substantially five minutes, quenching said'heated plate in a bath containing a non-oxidizing liquid, thereafter heating said plate in an atmosphere containing `sulphur vapors to a temperature of substantially 425 C. for substantially iive minutes, and thereafter permitting said plate to cool. I

In testimony whereof I afl-lx my signature.

' SAMUEL RUBEN.-

lias been formed, quenching ino 

